Modified silane compounds

ABSTRACT

This invention relates to the reversible protection of hydroxy-silane functional groups by acid cleavable protecting groups. The development of reversible protecting groups greatly enhances the current utility of silanes while introducing further novel applications. For instance, reversibly protected silanes are of particular value in applications where room temperature cure and/or adhesion is of value, such as coatings, high resolution imaging, caulks, adhesives, sealents, gaskets, and silicones. Reversibly protected silanes can also be beneficially used in reticulating agents, and in sizing agents, tires, and release coatings. The incorporation of reversibly protected silanes into coating resins is of particular value. The reversibly protected silane can be incorporated into the coating resin by polymerizing a monomer containing the reversibly protected silane into the resin or by post-addition into the coating formulation. The reversibly protected silane remains protected under basic conditions, such as in a coating formulation that contains a volatile base, for instance ammonium hydroxide. However, deprotection occurs under mildly acidic conditions. Thus, as a coating formulation containing a volatile base dries the volatile base evaporates and deprotection occurs. This allows for controlled room temperature crosslinking to occur with hydroxy-functionalized polymers. The present invention more specifically discloses a modified silane compound consisting of a silane having 3 or 4 acetal moieties bonded thereto.

This is a divisional of U.S. patent application Ser. No. 10/222,739,filed on Aug. 16, 2002, which claims the benefit of U.S. ProvisionalApplication Ser. No. 60/312,851, filed on Aug. 16, 2001, and U.S.Provisional Application Ser. No. 60/326,042, filed on Sep. 28, 2001.

BACKGROUND OF THE INVENTION

Most conventional coating resins are insoluble in water. Therefore, ingeneral practice, they have been dissolved in a suitable organic solventor dispersed in water with the aid of an emulsifying agent or surfactantin order to provide a coating composition suitable for application to asubstrate surface. A serious disadvantage of organic solvent solutionsis that they are potentially toxic, flammable and environmentalpollutants. Water-reducible coatings greatly reduce the magnitude ofthese problems. For this reason, water-based paints are currently beingused as a replacement for oil-based paints in many applications.

Various water-reducible coating resins, such as the one described inU.S. Pat. No. 4,474,926, have been developed. Water-reducible coatingsthat utilize such resins have been developed for a variety of purposesand have been widely accepted in many applications such as highwaystriping paint.

U.S. Pat. No. 4,968,741 describes a coating for metal substrates whichprovides improved corrosion and rust resistance. Such coatings are ofthe water-reducible type and can be beneficially utilized in theautomotive industry and other applications where good rust resistance isneeded. For instance, such coatings are excellent for coating bridgesand other outdoor metal structures.

It is also critical for coatings made with water-reducible coatingformulations to offer the desired combination of physical and chemicalproperties. For instance, in many applications, it is important for thecoating to exhibit excellent flexibility, excellent ultra-violet lightresistance and excellent solvent resistance. In applications whichinvolve metal substrates, outstanding corrosion and rust-resistance isnormally also sought.

For purposes of this patent application, an aqueous coating system isconsidered to be a colloidal dispersion of a resin in water which can bereduced by the addition of water and which forms a durable coating whenapplied to a substrate surface. The term aqueous coating system is usedherein interchangeably with the term water-reducible coating. Othernames which are sometimes applied to water-reducible coatings arewater-born, water-solubilized and water-dilutable.

SUMMARY OF THE INVENTION

This invention relates to the reversible protection of hydroxy-silanefunctional groups by acid cleavable protecting groups. The developmentof reversible protecting groups greatly enhances the current utility ofsilanes while introducing further novel applications. For instance,reversibly protected silanes are of particular value in applicationswhere room temperature cure and/or adhesion is of value, such as highresolution imaging, caulks, adhesives, sealents, gaskets, and silicones.Reversibly protected silanes can also be beneficially used inreticulating agents, and in sizing agents, tires, and release coatings.

The incorporation of reversibly protected silanes into coating resins isof particular value. The reversibly protected silane can be incorporatedinto the coating resin by polymerizing a monomer containing thereversibly protected silane into the resin or by post-addition into thecoating formulation. The reversibly protected silane remains protectedunder basic conditions, such as in a coating formulation that contains avolatile base, for instance ammonium hydroxide. However, deprotectionoccurs under mildly acidic conditions. Thus, as a coating formulationcontaining a volatile base dries the volatile base evaporates anddeprotection occurs. This allows for controlled room temperaturecrosslinking to occur with hydroxy-functionalized polymers. Chemicaladhesion to hydroxy-group containing substrates, such as metal, glass,and wood, also occurs. This makes coating resins that contain reversiblyprotected silanes especially valuable for coating metals, glass, andwood. Since such coating formulations that contain reversibly protectedsilanes are curable at room temperature they are much easier to applyand cure than conventional systems. Benefits associated with usingcoating formulations that contain reversibly protected silanes arerealized in a wide variety of applications including structuralcoatings, anti-corrosion coatings, and marine biofouling coatings.

This invention further relates to the synthesis of a latex which can beused in making self-crosslinking water-reducible coating compositions,such as paints, which offer excellent solvent resistance, reduced dryingtime and improved adhesion to metal and glass. Coatings which areformulated with the latex of this invention are environmentallyadvantageous because they contain no or extremely low levels of volatileorganic compounds and additionally offer excellent flexibility andexcellent ultra-violet light resistance.

The present invention more specifically discloses a water-reduciblecoating composition which is comprised of (1) water; (2) a resin havingrepeat units which are derived from (a) about 30 to about 75 weightpercent vinyl aromatic monomers, (b) about 20 to about 65 weight percentof alkyl acrylate monomers, (c) about 1 to about 8 weight percent alkylpropenoic acid monomers and (d) about 0.5 to about 5 weight percentreversibly protected silane monomers, based on 100 weight percentmonomers; (3) a wetting agent; and (4) a defoamer.

The subject invention further reveals a process for producing aneutralized latex that is useful in the manufacture ofself-crosslinkable water-reducible coatings which comprises: (1) freeradical aqueous emulsion polymerizing at a pH of less than about 3.5, amonomer mixture which comprises, based on 100 weight percent monomers:(a) from about 30 to about 75 weight percent vinyl aromatic monomers,(b) from about 20 to about 65 weight percent of alkyl acrylate monomers,(c) from about 1 to about 8 weight percent alkyl propenoic acid monomersand (d) about 0.5 to about 5 weight percent reversibly protected silanemonomers; in the presence of about 0.2 to 3 phm of at least one α-olefinsulfonate soap to produce a latex; and (2) neutralizing the latex withammonia to a pH which is within the range of about 7 to about 10.5 toproduce the neutralized latex.

The present invention also discloses a latex which is useful in themanufacture of self-crosslinkable water-reducible coatings, said latexbeing comprised of (1) water, (2) an emulsifier and (3) a polymer whichis comprised of repeat units which are derived from (a) about 30 toabout 75 weight percent vinyl aromatic monomers, (b) about 20 to about65 weight percent of alkyl acrylate monomers, (c) about 1 to about 8weight percent alkyl propenoic acid monomers and (d) about 0.5 to about5 weight percent reversibly protected silane monomers.

The present invention further discloses a modified silane compoundconsisting of a silane having 3 or 4 acetal moieties bonded thereto.

The present invention further discloses a modified silane compoundconsisting of silane having 2 acetal moieties bonded thereto with theproviso that the silane compound does not contain a methyl, ethyl, orphenyl group if the silane compound has the following structure:

wherein n represents an integer.

The present invention further discloses a modified silane compoundhaving a structural formula selected from the group consisting of:

wherein n represents an integer from 2 to 4; wherein m represents aninteger from 1 to about 20; with the proviso that m can represent theinteger 0 for structures of formula (3) wherein Z represents the groupC(R)R′; wherein X groups can be the same or different; wherein Xrepresents a chemical moiety; with the proviso that X does not representa methyl group, an ethyl group, or a phenyl group in cases where themodified silane compound is of structural formula (2) wherein nrepresents the integer 1 or the integer 2 wherein R* represents ahydrogen atom wherein Y represents an oxygen atom wherein Z representsthe moiety C(R)R′; wherein R, R′, and R″ can be the same or differentand are selected from the group consisting of hydrogen atoms, alkylgroups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R* is selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein R, R′, R″, and R*can be bonded together in any combination in cases where R, R′, R″, andR* are not hydrogen atoms, halide atoms, or hydroxy groups; wherein Yrepresents a moiety selected from the group consisting of C(R)R′,oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; with the proviso that Y and Z can not both represent themoiety C(R)R′; wherein the contiguous cyclic ring in formulas (1) and(3) can contain heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon in cases where mrepresents an integer greater than 1; wherein the contiguous cyclic ringin formulas (1) and (3) can be saturated or unsaturated in cases where mrepresents an integer greater than 1; wherein said alkyl groups, arylgroups, alkaryl groups, and alkoxy groups can contain halide atoms andheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon.

The present invention further discloses a modified silane compoundhaving a structural formula selected from the group consisting of:

wherein m represents an integer from 1 to about 20; with the provisothat m can represent the integer 0 for structures of formula (3) whereinZ represents the group C(R)R′ wherein X represents a chemical moietyother than a methyl group; wherein X groups can be the same ordifferent; wherein X represents a chemical moiety other than a methyl,ethyl, butyl, or phenyl in cases where the modified silane compound isof structural formula (1) wherein Y represents an oxygen atom wherein Zrepresents the moiety C(R)R′ wherein m in equal to the integer 2 or theinteger 3; wherein X represents a chemical moiety other than a methylgroup, a tertiary butyl group, or a phenyl group in cases where themodified silane compound is of structural formula (3) wherein Yrepresents an oxygen atom wherein Z represents the moiety C(R)R′ whereinm in equal to the integer 3; wherein R, R′, and R″ can be the same ordifferent and are selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R* is selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein R, R′, R″, and R*can be bonded together in any combination in cases where R, R′, R″, andR* are not hydrogen atoms, halide atoms, or hydroxy groups; wherein Yrepresents a moiety selected from the group consisting of C(R)R′,oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; with the proviso that Y and Z can not both represent themoiety C(R)R′; wherein the contiguous cyclic ring in formulas (1) and(3) may contain heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon in cases where mrepresents an integer greater than 1; wherein the contiguous cyclic ringin formulas (1) and (3) may be saturated or unsaturated in cases where mrepresents an integer greater than 1; wherein said alkyl groups, arylgroups, alkaryl groups, and alkoxy groups can contain halide atoms andheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon.

The present invention further discloses a monomer having a structuralformula selected from the group consisting of:

wherein n represents an integer from 1 to 3; wherein m represents aninteger from 1 to about 20; with the proviso that m can represent theinteger 0 for structures of formula (3) wherein Z represents the groupC(R)R′; wherein X′ groups can be the same or different; wherein X′represents an unsaturated moiety containing at least one non-aromaticdouble bond; wherein R, R′, and R″ can be the same or different and areselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms, hydroxy groups, and halide atoms; wherein R* is selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, and alkaryl groups containing from 7 to about 18carbon atoms; wherein R, R′, R″, and R* can be bonded together in anycombination in cases where R, R′, R″, and R* are not hydrogen atoms,halide atoms, or hydroxy groups; wherein Y represents a moiety selectedfrom the group consisting of C(R)R′, oxygen, sulfur, nitrogen, andphosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; with theproviso that Y and Z can not both represent the moiety C(R)R′; whereinthe contiguous cyclic ring in formulas (1) and (3) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1) and(3) can be saturated or unsaturated in cases where m represents aninteger greater than 1; wherein said alkyl groups, aryl groups, alkarylgroups, and alkoxy groups can contain halide atoms and heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon.

The present invention further discloses a polymer which is comprised ofpolymer chains having at least one modified silane moiety bondedthereto, wherein said modified silane moiety is of a structural formulaselected from the group consisting of:

wherein n represents an integer from 1 to 3; wherein m represents aninteger from 1 to about 20; with the proviso that m can represent theinteger 0 for structures of formula (3) wherein Z represents the groupC(R)R′; wherein X″ groups can be the same or different; wherein X″represents a chemical moiety; wherein R, R′, and R″ can be the same ordifferent and are selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R* is selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein R, R′, R″, and R*can be bonded together in any combination in cases where R, R′, R″, andR* are not hydrogen atoms, halide atoms, or hydroxy groups; wherein Yrepresents a moiety selected from the group consisting of C(R)R′,oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; with the proviso that Y and Z can not both represent themoiety C(R)R′; wherein the contiguous cyclic ring in formulas (1) and(3) can contain heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon in cases where mrepresents an integer greater than 1; wherein the contiguous cyclic ringin formulas (1) and (3) can be saturated or unsaturated in cases where mrepresents an integer greater than 1; wherein said alkyl groups, arylgroups, alkaryl groups, and alkoxy groups can contain halide atoms andheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon.

The present invention further discloses a modified silane compoundhaving a structural formula selected from the group consisting of:

wherein m represents an integer from 1 to about 20; wherein X groups canbe the same or different; wherein X represents a chemical moiety;wherein Q is selected from the group consisting of hydrogen atoms andSiX₃; wherein R and R′ can be the same or different and are selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, alkaryl groups containing from 7 to about 18carbon atoms, alkoxy groups containing from 1 to about 18 carbon atoms,hydroxy groups, and halide atoms; wherein R* is selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, and alkaryl groups containing from 7 to about 18 carbon atoms;wherein R, R′, and R* can be bonded together in any combination in caseswhere R, R′, and R* are not hydrogen atoms, halide atoms, or hydroxygroups; wherein Y represents a moiety selected from the group consistingof oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents amoiety selected from the group consisting of C(R)R′, oxygen, sulfur,nitrogen, and phosphorus; wherein the contiguous cyclic ring in formulas(1), (2), (3), (4), (5), (6), (7), (8), (9), and (10) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), (6), (7), (8), (9), and (10) can be saturated orunsaturated in cases where m represents an integer greater than 1;wherein said alkyl groups, aryl groups, alkaryl groups, and alkoxygroups can contain halide atoms and heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon.

The present invention further discloses a monomer having a structuralformula selected from the group consisting of:

wherein m represents an integer from 1 to about 20; wherein X′ groupscan be the same or different; wherein X′ represents an unsaturatedmoiety containing at least one non-aromatic double bond; wherein Q isselected from the group consisting of hydrogen atoms and SiX′₃; whereinR and R′ can be the same or different and are selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, alkaryl groups containing from 7 to about 18 carbon atoms, alkoxygroups containing from 1 to about 18 carbon atoms, hydroxy groups, andhalide atoms; wherein R* is selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, andalkaryl groups containing from 7 to about 18 carbon atoms; wherein R,R′, and R* can be bonded together in any combination in cases where R,R′, and R* are not hydrogen atoms, halide atoms, or hydroxy groups;wherein Y represents a moiety selected from the group consisting ofoxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), (6), (7), (8), (9), and (10) can contain heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon in cases where m represents an integer greaterthan 1; wherein the contiguous cyclic ring in formulas (1), (2), (3),(4), (5), (6), (7), (8), (9), and (10) can be saturated or unsaturatedin cases where m represents an integer greater than 1; wherein saidalkyl groups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon.

The present invention further discloses a polymer which is comprised ofpolymer chains having at least one modified silane moiety bondedthereto, wherein said modified silane moiety is of a structural formulaselected from the group consisting of:

wherein m represents an integer from 1 to about 20; wherein X″ groupscan be the same or different; wherein X″ represents a chemical moiety;wherein Q is selected from the group consisting of hydrogen atoms andX″₂Si—; wherein R and R′ can be the same or different and are selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, alkaryl groups containing from 7 to about 18carbon atoms, alkoxy groups containing from 1 to about 18 carbon atoms,hydroxy groups, and halide atoms; wherein R* is selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, and alkaryl groups containing from 7 to about 18 carbon atoms;wherein R, R′, and R* can be bonded together in any combination in caseswhere R, R′, R″, and R* are not hydrogen atoms, halide atoms, or hydroxygroups; wherein Y represents a moiety selected from the group consistingof oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents amoiety selected from the group consisting of C(R)R′, oxygen, sulfur,nitrogen, and phosphorus; wherein the contiguous cyclic ring in formulas(1), (2), (3), (4), (5), (6), (7), (8), (9), and (10) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), (6), (7), (8), (9), and (10) can be saturated orunsaturated in cases where m represents an integer greater than 1;wherein said alkyl groups, aryl groups, alkaryl groups, and alkoxygroups can contain halide atoms and heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon.

The present invention further discloses an acetal compound having astructural formula selected from the group consisting of:

wherein M represents an atom selected from the group consisting of Ge,Sn, Pb, Ti, and Zr; wherein n represents an integer from 1 to 4; whereinm represents an integer from 1 to about 20; with the proviso that m canrepresent the integer 0 for structures of formula (3) wherein Zrepresents the group C(R)R′; wherein X groups can be the same ordifferent; wherein X represents a chemical moiety; wherein R, R′, and R″can be the same or different and are selected from the group consistingof hydrogen atoms, alkyl groups containing from 1 to about 12 carbonatoms, aryl groups containing from about 6 to about 18 carbon atoms,alkaryl groups containing from 7 to about 18 carbon atoms, alkoxy groupscontaining from 1 to about 18 carbon atoms, hydroxy groups, and halideatoms; wherein R* is selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, and alkarylgroups containing from 7 to about 18 carbon atoms; wherein R, R′, R″,and R* can be bonded together in any combination in cases where R, R′,R″, and R* are not hydrogen atoms, halide atoms, or hydroxy groups;wherein Y represents a moiety selected from the group consisting ofC(R)R′, oxygen, sulfur, nitrogen, and phosphorus; wherein Z represents amoiety selected from the group consisting of C(R)R′, oxygen, sulfur,nitrogen, and phosphorus; with the proviso that Y and Z can not bothrepresent the moiety C(R)R′; wherein the contiguous cyclic ring informulas (1) and (3) can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon in caseswhere m represents an integer greater than 1; wherein the contiguouscyclic ring in formulas (1) and (3) can be saturated or unsaturated incases where m represents an integer greater than 1; wherein said alkylgroups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon.

The present invention further discloses an acetal compound having astructural formula selected from the group consisting of:

wherein M represents an atom selected from the group consisting of Ge,Sn, Pb, Ti, and Zr; wherein m represents an integer from 1 to about 20;wherein X groups can be the same or different; wherein X represents achemical moiety; wherein Q is selected from the group consisting ofhydrogen atoms and MX₃; wherein R and R′ can be the same or differentand are selected from the group consisting of hydrogen atoms, alkylgroups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R* is selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein R, R′, and R* can bebonded together in any combination in cases where R, R′, and R* are nothydrogen atoms, halide atoms, or hydroxy groups; wherein Y represents amoiety selected from the group consisting of oxygen, sulfur, nitrogen,and phosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; whereinthe contiguous cyclic ring in formulas (1), (2), (3), (4), (5), (6),(7), (8), (9), and (10) can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon in caseswhere m represents an integer greater than 1; wherein the contiguouscyclic ring in formulas (1), (2), (3), (4), (5), (6), (7), (8), (9), and(10) can be saturated or unsaturated in cases where m represents aninteger greater than 1; wherein said alkyl groups, aryl groups, alkarylgroups, and alkoxy groups can contain halide atoms and heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon.

The present invention further discloses a process for synthesizing amodified silane which comprises reacting a cyclic hemiacetal having astructural formula selected from the group consisting of:

wherein m represents an integer from 1 to about 20; wherein R and R′ canbe the same or different and are selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, alkarylgroups containing from 7 to about 18 carbon atoms, alkoxy groupscontaining from 1 to about 18 carbon atoms, hydroxy groups, and halideatoms; wherein R* is selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, and alkarylgroups containing from 7 to about 18 carbon atoms; wherein R, R′, and R*can be bonded together in any combination in cases where R, R′, and R*are not hydrogen atoms, halide atoms, or hydroxy groups; wherein Yrepresents a moiety selected from the group consisting of oxygen,sulfur, nitrogen, and phosphorus; wherein Z represents a moiety selectedfrom the group consisting of C(R)R′, oxygen, sulfur, nitrogen, andphosphorus; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), and (6) can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon in caseswhere m represents an integer greater than 1; wherein the contiguouscyclic ring in formulas (1), (2), (3), (4), (5), and (6) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;with a silicon containing compound of the structural formula:X_(4-n)Si

OR″]_(n)wherein n represents an integer from 1 to 4; wherein R″ is selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinsaid alkyl groups, aryl groups, alkaryl groups, and alkoxy groups cancontain halide atoms and heteroatoms selected from the group consistingof oxygen, sulfur, nitrogen, phosphorus, and silicon; wherein Xrepresents a chemical moiety; wherein said process is conducted at atemperature which is within the range of about 10° C. to about 50° C.,wherein said process is conducted at a pressure which is within therange of about 25 torr to about 75 torr, and wherein said process isconducted in the presence of an alcohol salt of the structural formulaM′OR′″ wherein M′ represents a Group Ia metal and wherein R′″ representsan alkyl group containing from 1 to 10 carbon atoms.

The present invention further discloses a process for synthesizing amodified silane which comprises reacting a cyclic hemiacetal having astructural formula selected from the group consisting of:

wherein m represents an integer from 1 to about 20; wherein R and R′ canbe the same or different and are selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, alkarylgroups containing from 7 to about 18 carbon atoms, alkoxy groupscontaining from 1 to about 18 carbon atoms, hydroxy groups, and halideatoms; wherein R* is selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, and alkarylgroups containing from 7 to about 18 carbon atoms; wherein R, R′, and R*can be bonded together in any combination in cases where R, R′, and R*are not hydrogen atoms, halide atoms, or hydroxy groups; wherein Yrepresents a moiety selected from the group consisting of oxygen,sulfur, nitrogen, and phosphorus; wherein Z represents a moiety selectedfrom the group consisting of C(R)R′, oxygen, sulfur, nitrogen, andphosphorus; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), and (6) can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon in caseswhere m represents an integer greater than 1; wherein the contiguouscyclic ring in formulas (1), (2), (3), (4), (5), and (6) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;with a silicon containing compound of the structural formula:X_(4-n)Si

OR″]_(n)wherein n represents an integer from 1 to 4; wherein R″ is selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinsaid alkyl groups, aryl groups, alkaryl groups, and alkoxy groups cancontain halide atoms and heteroatoms selected from the group consistingof oxygen, sulfur, nitrogen, phosphorus, and silicon; wherein Xrepresents a chemical moiety; wherein said process is conducted at atemperature which is within the range of about 10° C. to about 50° C.,wherein said process is conducted at a pressure which is within therange of about 25 torr to about 75 torr, and wherein said process isconducted in the presence of an alcohol salt of the structural formulaM′OR′″ wherein M′ represents a Group Ia metal and wherein R′″ representsan alkyl group containing from 1 to 10 carbon atoms.

The present invention further discloses a process for synthesizing amodified silane which comprises reacting a cyclic hemiacetal of thestructural formula:

wherein R and R′ can be the same or different and are selected from thegroup consisting of hydrogen atoms, alkyl groups containing from 1 toabout 12 carbon atoms, aryl groups containing from about 6 to about 18carbon atoms, and alkaryl groups containing from 7 to about 18 carbonatoms; with a silicon containing compound of the structural formula:X_(4-n)Si

OR″]_(n)wherein n represents an integer from 1 to 4; wherein R″ represents analkyl group containing from 1 to about 10 carbon atoms, wherein Xrepresents a chemical moiety other than a hydrogen atom or a halogen;wherein said process is conducted at a temperature which is within therange of about 10° C. to about 50° C., wherein said process is conductedat a pressure which is within the range of about 25 torr to about 75torr, and wherein said process is conducted in the presence of analcohol salt of the structural formula M′OR′″ wherein M′ represents aGroup Ia metal and wherein R′″ represents an alkyl group containing from1 to 10 carbon atoms.

The present invention further discloses a process for synthesizing amodified silane which comprises reacting a cyclic hemiacetal selectedfrom the group consisting of tetrahydropyran-2-ol andtetrahydrofuran-2-ol; with a silicon containing compound selected fromthe group consisting of tetramethylorthosilicate andtetraethylorthosilicate; wherein said process is conducted at atemperature which is within the range of about 10° C. to about 50° C.,wherein said process is conducted at a pressure which is within therange of about 25 torr to about 75 torr, and wherein said process isconducted in the presence of an alcohol salt of the structural formulaM′OR′″ wherein M′ represents a Group Ia metal and wherein R′″ representsan alkyl group containing from 1 to 2 carbon atoms.

The present invention further discloses a process for synthesizing amodified silane which comprises reacting a cyclic hemiacetal having astructural formula selected from the group consisting of:

wherein m represents an integer from 1 to about 20; wherein R and R′ canbe the same or different and are selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, alkarylgroups containing from 7 to about 18 carbon atoms, alkoxy groupscontaining from 1 to about 18 carbon atoms, hydroxy groups, and halideatoms; wherein R* is selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, and alkarylgroups containing from 7 to about 18 carbon atoms; wherein R, R′, and R*can be bonded together in any combination in cases where R, R′, and R*are not hydrogen atoms, halide atoms, or hydroxy groups; wherein Yrepresents a moiety selected from the group consisting of oxygen,sulfur, nitrogen, and phosphorus; wherein Z represents a moiety selectedfrom the group consisting of C(R)R′, oxygen, sulfur, nitrogen, andphosphorus; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), and (6) can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon in caseswhere m represents an integer greater than 1; wherein the contiguouscyclic ring in formulas (1), (2), (3), (4), (5), and (6) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;with a silicon containing compound of the structural formula:X_(4-n)Si

X*]_(n)wherein n represents an integer from 1 to 4; wherein X* represents ahalide atom; wherein X represents a chemical moiety; wherein saidprocess is conducted in the presence of an amine containing compound.

The present invention further discloses a process for synthesizing amodified silane which comprises reacting a cyclic hemiacetal having astructural formula selected from the group consisting of:

wherein m represents an integer from 1 to about 20; wherein R and R′ canbe the same or different and are selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, alkarylgroups containing from 7 to about 18 carbon atoms, alkoxy groupscontaining from 1 to about 18 carbon atoms, hydroxy groups, and halideatoms; wherein R* is selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, and alkarylgroups containing from 7 to about 18 carbon atoms; wherein R, R′, and R*can be bonded together in any combination in cases where R, R′, and R*are not hydrogen atoms, halide atoms, or hydroxy groups; wherein Yrepresents a moiety selected from the group consisting of oxygen,sulfur, nitrogen, and phosphorus; wherein Z represents a moiety selectedfrom the group consisting of C(R)R′, oxygen, sulfur, nitrogen, andphosphorus; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), and (6) can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon in caseswhere m represents an integer greater than 1; wherein the contiguouscyclic ring in formulas (1), (2), (3), (4), (5), and (6) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;with a silicon containing compound of the structural formula:X_(4-n)Si

X*]_(n)wherein n represents an integer from 1 to 4; wherein X* represents ahalide atom; wherein X represents a chemical moiety; wherein saidprocess is conducted in the presence of an amine containing compound.

The present invention further discloses a process for synthesizing amodified silane which comprises reacting a cyclic hemiacetal of thestructural formula:

wherein R and R′ can be the same or different and are selected from thegroup consisting of hydrogen atoms, alkyl groups containing from 1 toabout 12 carbon atoms, aryl groups containing from about 6 to about 18carbon atoms, and alkaryl groups containing from 7 to about 18 carbonatoms; with a silicon containing compound of the structural formula:X_(4-n)—Si—X*_(n)wherein n represents an integer from 1 to 4; wherein X* represents ahalide atom; wherein X represents a chemical moiety; wherein saidprocess is conducted in the presence of an amine containing compound.

22. A process for synthesizing a modified silane which comprisesreacting a vinyl ether compound having a structural formula selectedfrom the group consisting of:

wherein m represents an integer from 1 to about 20; wherein R, R′, andR″ can be the same or different and are selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, alkaryl groups containing from 7 to about 18 carbon atoms, alkoxygroups containing from 1 to about 18 carbon atoms, hydroxy groups, andhalide atoms; wherein R, R′, and R″ can be bonded together in anycombination in cases where R, R′, and R″ are not hydrogen atoms, halideatoms, or hydroxy groups; wherein the contiguous cyclic ring in formulas(2) can contain heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon in cases where mrepresents an integer greater than 1; wherein the contiguous cyclic ringin formulas (2) can be saturated or unsaturated in cases where mrepresents an integer greater than 1; wherein said alkyl groups, arylgroups, alkaryl groups, and alkoxy groups can contain halide atoms andheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon; with a silicon containing compound ofthe structural formula:X_(4-n)Si

OR*]_(n)wherein n represents an integer from 3 to 4; wherein R* is selected fromthe group consisting of alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, and alkaryl groups containing from 7 to about 18 carbon atoms;wherein said alkyl groups, aryl groups, alkaryl groups, and alkoxygroups can contain halide atoms and heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon; whereinX represents a chemical moiety; wherein said process is conducted in thepresence of an acid.

The present invention further discloses a process for synthesizing amodified silane which comprises reacting a ester compound having astructural formula selected from the group consisting of:

wherein m represents an integer from 1 to about 20; wherein R, R′, andR″ can be the same or different and are selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, alkaryl groups containing from 7 to about 18 carbon atoms, alkoxygroups containing from 1 to about 18 carbon atoms, hydroxy groups, andhalide atoms; wherein R* is selected from the group consisting of alkylgroups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein R, R′, R″, and R*can be bonded together in any combination in cases where R, R′, R″, andR* are not hydrogen atoms, halide atoms, or hydroxy groups; wherein thecontiguous cyclic ring in formulas (2) can contain heteroatoms selectedfrom the group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon in cases where m represents an integer greater than 1; whereinthe contiguous cyclic ring in formulas (2) can be saturated orunsaturated in cases where m represents an integer greater than 1;wherein said alkyl groups, aryl groups, alkaryl groups, and alkoxygroups can contain halide atoms and heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon; with asilicon containing compound of the structural formula:X_(4-n)Si

X*]_(n)wherein n represents an integer from 2 to 4; wherein X* is leaving groupselected from the group consisting of halide atoms, triflate, andtosylate; wherein X represents a chemical moiety; wherein said processis conducted in the presence of the reducing agent diisobutylaluminumhydride; wherein said process is conducted in the presence of an aminecontaining compound.

The present invention further discloses an aqueous polymer compositionsuitable for use as an adhesive, caulk, sealant, or coating which iscomprised of (1) an acid; (2) a volatile base; wherein the amount ofvolatile base present is sufficient for the aqueous polymer compositionto have a pH greater than 7; (3) water; (4) a resin having repeat unitswhich are derived from (a) a member selected from the group consistingof vinyl monomers, vinyl aromatic monomers, conjugated diolefinmonomers, and acrylic monomers, (b) a monomer in accordance of claim 7;(5) a wetting agent; (6) a defoamer; and (7) a pigment, filler, andextender; with the proviso that the aqueous polymer composition can bevoid of said wetting agent, defoamer, pigment, filler, and extender.

The present invention further discloses an aqueous polymer compositionsuitable for use as an adhesive, caulk, sealant, or coating which iscomprised of (1) an acid; (2) a volatile base; wherein the amount ofvolatile base present is sufficient for the aqueous polymer compositionto have a pH greater than 7; (3) water; (4) a resin having repeat unitswhich are derived from (a) a member selected from the group consistingof vinyl monomers, vinyl aromatic monomers, conjugated diolefinmonomers, and acrylic monomers, (b) a monomer in accordance of claim 11;(5) a wetting agent; (6) a defoamer; and (7) a pigment, filler, andextender; with the proviso that the aqueous polymer composition can bevoid of said wetting agent, defoamer, pigment, filler, and extender.

The present invention further discloses an aqueous polymer compositionsuitable for use as an adhesive, caulk, sealant, or coating which iscomprised of (1) an acid; (2) a volatile base selected from the groupconsisting of NR¹R²R³R⁴OH; wherein R¹, R², R³, and R⁴ can be the same ordifferent and are selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms; R¹, R², R³, and R⁴ can be bondedtogether in any combination in cases where R¹, R², R³, and R⁴ are nothydrogen atoms; wherein said alkyl groups, aryl groups, alkaryl groups,and alkoxy groups can contain halide atoms and heteroatoms selected fromthe group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon; wherein the amount of volatile base present is sufficient forthe aqueous polymer composition to have a pH greater than 7; (3) water;(4) a resin having repeat units which are derived from (a) a memberselected from the group consisting of vinyl monomers, vinyl aromaticmonomers, conjugated diolefin monomers, and acrylic monomers, (b) amonomer having a structural formula selected from the group consistingof:

wherein n represents an integer from 1 to 3; wherein m represents aninteger from 1 to about 20; with the proviso that m can represent theinteger 0 for structures of formula (3) wherein Z represents the groupC(R)R′; wherein X′ groups can be the same or different; wherein X′represents an unsaturated moiety containing at least one non-aromaticdouble bond; wherein R, R′, and R″ can be the same or different and areselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms, hydroxy groups, and halide atoms; wherein R* is selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, and alkaryl groups containing from 7 to about 18carbon atoms; wherein R, R′, R″, and R* can be bonded together in anycombination in cases where R, R′, R″, and R* are not hydrogen atoms,halide atoms, or hydroxy groups; wherein Y represents a moiety selectedfrom the group consisting of C(R)R′, oxygen, sulfur, nitrogen, andphosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; with theproviso that Y and Z can not both represent the moiety C(R)R′; whereinthe contiguous cyclic ring in formulas (1) and (3) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1) and(3) can be saturated or unsaturated in cases where m represents aninteger greater than 1; wherein said alkyl groups, aryl groups, alkarylgroups, and alkoxy groups can contain halide atoms and heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon; (5) a wetting agent; and (6) a defoamer.

The present invention further discloses a n aqueous polymer compositionsuitable for use as an adhesive, caulk, sealant, or coating which iscomprised of (1) an acid; (2) a volatile base selected from the groupconsisting of NR¹R²R³R⁴OH; wherein R¹, R ², R³, and R can be the same ordifferent and are selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms; wherein R¹, R², R³,and R⁴ can be bondedtogether in any combination in cases where R¹, R², R³, and R⁴ are nothydrogen atoms; wherein said alkyl groups, aryl groups, alkaryl groups,and alkoxy groups can contain halide atoms and heteroatoms selected fromthe group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon; wherein the amount of volatile base present is sufficient forthe aqueous polymer composition to have a pH greater than 7; (3) water;(4) a resin having repeat units which are derived from (a) a memberselected from the group consisting of vinyl monomers, vinyl aromaticmonomers, conjugated diolefin monomers, and acrylic monomers, and (b) amonomer having a structural formula selected from the group consistingof:

wherein n represents an integer from 1 to 3; wherein m represents aninteger from 1 to about 20; wherein X″ groups can be the same ordifferent; wherein X″ represents an unsaturated moiety containing atleast one non-aromatic double bond; wherein R, R′, and R″ can be thesame or different and are selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R, R′, and R″ can be bonded together in any combination in caseswhere R, R′, and R″ are not hydrogen atoms, halide atoms, or hydroxygroups; wherein the contiguous cyclic ring in formula (1) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formula (1) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;(5) a wetting agent; and (6) a defoamer.

The present invention further discloses an aqueous polymer compositionsuitable for use as an adhesive, caulk, sealant, or coating which iscomprised of (1) an acid (2) a volatile base selected from the groupconsisting of NR¹R²R³R⁴OH; wherein R¹, R², R³, and R⁴ can be the same ordifferent and are selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms; wherein R¹, R², R³, and R⁴ can bebonded together in any combination in cases R¹, R², R³, and R⁴ are nothydrogen atoms; wherein said alkyl groups, aryl groups, alkaryl groups,and alkoxy groups can contain halide atoms and heteroatoms selected fromthe group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon; wherein the amount of volatile base present is sufficient forthe aqueous polymer composition to have a pH greater than 7; (3) water;(4) a resin having repeat units which are derived from (a) a memberselected from the group consisting of vinyl monomers, vinyl aromaticmonomers, conjugated diolefin monomers, and acrylic monomers, and (b) amonomer consisting of the following structure:

and (5) a wetting agent; and (6) a defoamer.

The present invention further discloses an organic solvent based polymercomposition suitable for use as an adhesive, caulk, sealant, or coatingwhich is comprised of (1) an organic solvent; (2) an acid; (3) avolatile base selected from the group consisting of NR¹R²R³R⁴OH; whereinR¹, R², R³, and R⁴ can be the same or different and are selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinR¹, R², R³, and R⁴ can be bonded together in any combination in caseswhere R¹, R², R³, and R⁴ are not hydrogen atoms; wherein said alkylgroups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon; wherein the amount ofvolatile base present is sufficient for the organic solvent basedpolymer composition to be rendered basic; (4) a resin having repeatunits which are derived from (a) a member selected from the groupconsisting of vinyl monomers, vinyl aromatic monomers, conjugateddiolefin monomers, and acrylic monomers, and (b) a monomer having astructural formula selected from the group consisting of:

wherein n represents an integer from 1 to 3; wherein m represents aninteger from 1 to about 20; with the proviso that m can represent theinteger 0 for structures of formula (3) wherein Z represents the groupC(R)R′; wherein X′ groups can be the same or different; wherein X′represents an unsaturated moiety containing at least one non-aromaticdouble bond; wherein R, R′, and R″ can be the same or different and areselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms, hydroxy groups, and halide atoms; wherein R* is selectedfrom the group consisting of hydrogen atoms, alkyl groups containingfrom 1 to about 12 carbon atoms, aryl groups containing from about 6 toabout 18 carbon atoms, and alkaryl groups containing from 7 to about 18carbon atoms; wherein R, R′, R″, and R* can be bonded together in anycombination in cases where R, R′, R″, and R* are not hydrogen atoms,halide atoms, or hydroxy groups; wherein Y represents a moiety selectedfrom the group consisting of C(R)R′, oxygen, sulfur, nitrogen, andphosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; with theproviso that Y and Z can not both represent the moiety C(R)R′; whereinthe contiguous cyclic ring in formulas (1) and (3) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1) and(3) can be saturated or unsaturated in cases where m represents aninteger greater than 1; wherein said alkyl groups, aryl groups, alkarylgroups, and alkoxy groups can contain halide atoms and heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon; (5) a wetting agent; and (6) a defoamer.

The present invention further discloses an organic solvent based polymercomposition suitable for use as an adhesive, caulk, sealant, or coatingwhich is comprised of (1) an organic solvent; (2) an acid; (3) avolatile base selected from the group consisting NR¹R²R³R⁴OH; whereinR¹, R¹, R³, and R⁴ can be the same or different and are selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinR¹, R², R³, and R⁴ can be bonded together in any combination in caseswhere R¹, R², R³, and R⁴ are not hydrogen atoms; wherein said alkylgroups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon; wherein the amount ofvolatile base present is sufficient for the organic solvent basedpolymer composition to be rendered basic; (4) a resin having repeatunits which are derived from (a) a member selected from the groupconsisting of vinyl monomers, vinyl aromatic monomers, conjugateddiolefin monomers, and acrylic monomers, and (b) a monomer having astructural formula selected from the group consisting of:

wherein n represents an integer from 1 to 3; wherein m represents aninteger from 1 to about 20; wherein X′ groups can be the same ordifferent; wherein X′ represents an unsaturated moiety containing atleast one non-aromatic double bond; wherein R, R′, and R″ can be thesame or different and are selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R, R′, and R″ can be bonded together in any combination in caseswhere R, R′, and R″ are not hydrogen atoms, halide atoms, or hydroxygroups; wherein the contiguous cyclic ring in formula (1) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formula (1) can besaturated or unsaturated in cases where m represents an integer greaterthan 1; wherein said alkyl groups, aryl groups, alkaryl groups, andalkoxy groups can contain halide atoms and heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;(5) a wetting agent; and (6) defoamer.

The present invention further discloses an organic solvent based polymercomposition suitable for use as an adhesive, caulk, sealant, or coatingwhich is comprised of (1) an organic solvent; (2) an acid; (3) avolatile base selected from the group consisting of NR¹R²R³R⁴OH; whereinR¹, R², R³, and R⁴ can be the same or different and are selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinR¹, R², R³, and R⁴ can be bonded together in any combination in caseswhere R¹, R², R³, and R⁴ are not hydrogen atoms; wherein said alkylgroups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon; wherein the amount ofvolatile base present is sufficient for the organic solvent basedpolymer composition to be rendered basic; (4) a resin having repeatunits which are derived from (a) a member selected from the groupconsisting of vinyl monomers, vinyl aromatic monomers, conjugateddiolefin monomers, and acrylic monomers, and (b) a monomer consisting ofthe following structure:

and (5) a wetting agent; and (6) a defoamer.

The present invention further discloses a one-componentcondensation-crosslinking room-temperature vulcanizable silicone rubbercomposition comprising (1) silanol end-terminated organopolysiloxanebase polymer; (2) modified silane compound of claim 3; (3) an acid; (4)a volatile base selected from the group consisting NR¹R²R³R⁴OH; whereinR¹, R², R³, and R⁴ can be the same or different and are selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinR¹, R², R³, and R⁴ can be bonded together in any combination in caseswhere R¹, R², R³, and R⁴ are not hydrogen atoms; wherein said alkylgroups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon; wherein the amount ofvolatile base present is sufficient to render the one-componentcondensation-crosslinking room-temperature vulcanizable silicone rubbercomposition basic; and (5) a reinforcing particulate filler.

The present invention further discloses a one-componentcondensation-crosslinking room-temperature vulcanizable silicone rubbercomposition comprising (1) silanol end-terminated organopolysiloxanebase polymer; (2) modified silane compound of claim 9; (3) an acid; (4)a volatile base selected from the group consisting NR¹R²R³R⁴OH; whereinR¹, R², R³, and R⁴ can be the same or different and are selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinR¹, R², R³, and R⁴ can be bonded together in any combination in caseswhere R¹, R², R³, and R⁴ are not hydrogen atoms; wherein said alkylgroups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon; wherein the amount ofvolatile base present is sufficient to render the one-componentcondensation-crosslinking room-temperature vulcanizable silicone rubbercomposition basic; and (5) a reinforcing particulate filler.

The present invention further discloses a one-componentcondensation-crosslinking room-temperature vulcanizable silicone rubbercomposition comprising (1) silanol end-terminated organopolysiloxanebase polymer; (2) modified silane compound of claim 12 and claim 13; (3)an acid; (4) a volatile base selected from the group consistingNR¹R²R³R⁴OH; wherein R¹, R², R³, and R⁴ can be the same or different andare selected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, alkaryl groups containing from 7 toabout 18 carbon atoms, alkoxy groups containing from 1 to about 18carbon atoms; wherein R¹, R², R³, and R⁴ can be bonded together in anycombination in cases where R¹, R², R³, and R⁴ are not hydrogen atoms;wherein said alkyl groups, aryl groups, alkaryl groups, and alkoxygroups can contain halide atoms and heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon; whereinthe amount of volatile base present is sufficient to render theone-component condensation-crosslinking room-temperature vulcanizablesilicone rubber composition basic; and (5) a reinforcing particulatefiller.

The present invention also reveals a process for synthesizing a modifiedsilane which comprises reacting the salt of a cyclic hemiacetal having astructural formula selected from the group consisting of:

wherein A represents an alkali metal atom selected from the groupconsisting of lithium, sodium, and potassium; wherein m represents aninteger from 1 to about 20; wherein R and R′ can be the same ordifferent and are selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, and alkoxy groups containingfrom 1 to about 18 carbon atoms; wherein R* is selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, and alkaryl groups containing from 7 to about 18 carbon atoms;wherein R, R′, and R* can be bonded together in any combination in caseswhere R, R′, and R* are not hydrogen atoms; wherein Y represents amoiety selected from the group consisting of oxygen, sulfur, nitrogen,and phosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; whereinthe contiguous cyclic ring in formulas (1), (2), (3), (4), and (5) cancontain heteroatoms selected from the group consisting of oxygen,sulfur, nitrogen, phosphorus, and silicon in cases where m represents aninteger greater than 1; wherein the contiguous cyclic ring in formulas(1), (2), (3), (4), and (5) can be saturated or unsaturated in caseswhere m represents an integer greater than 1; wherein said alkyl groups,aryl groups, alkaryl groups, and alkoxy groups can contain heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon; with a silicon containing compound of thestructural formula:R″_(4-n)SiA′_(n)wherein n represents an integer from 1 to 4; wherein R″ is selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinsaid alkyl groups, aryl groups, alkaryl groups, and alkoxy groups cancontain heteroatoms selected from the group consisting of oxygen,sulfur, nitrogen, phosphorus, and silicon; wherein A′ represents ahalide atom selected from the group consisting of fluorine, chlorine,bromine, and iodine; wherein said process is conducted at a temperaturewhich is within the range of about −100° C. to about 50° C.

The subject invention further discloses a process for synthesizing amodified silane which comprises reacting the salt of a hemiacetal havinga structural formula selected from the group consisting of:

wherein A represents an alkali metal atom selected from the groupconsisting of lithium, sodium, and potassium; wherein m represents aninteger from 1 to about 20; wherein R and R′ can be the same ordifferent and are selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, and alkoxy groups containingfrom 1 to about 18 carbon atoms; wherein R* is selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, and alkaryl groups containing from 7 to about 18 carbon atoms;wherein R, R′, and R* can be bonded together in any combination in caseswhere R, R′, and R* are not hydrogen atoms; wherein Y represents amoiety selected from the group consisting of oxygen, sulfur, nitrogen,and phosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; whereinthe contiguous cyclic ring in formulas (1), (2), and (3) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1), (2),and (3) can be saturated or unsaturated in cases where m represents aninteger greater than 1; wherein said alkyl groups, aryl groups, alkarylgroups, and alkoxy groups can contain heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon;with a silicon containing compound of the structural formula:R″_(4-n)SiA′_(n)wherein n represents an integer from 1 to 4; wherein R″ is selected fromthe group consisting of hydrogen atoms, alkyl groups containing from 1to about 12 carbon atoms, aryl groups containing from about 6 to about18 carbon atoms, alkaryl groups containing from 7 to about 18 carbonatoms, alkoxy groups containing from 1 to about 18 carbon atoms; whereinsaid alkyl groups, aryl groups, alkaryl groups, and alkoxy groups cancontain heteroatoms selected from the group consisting of oxygen,sulfur, nitrogen, phosphorus, and silicon; wherein A′ represents ahalide atom selected from the group consisting of fluorine, chlorine,bromine, and iodine; wherein said process is conducted at a temperaturewhich is within the range of about −100° C. to about 50° C.

The present invention also reveals a process for synthesizing a modifiedsilane which comprises reacting the salt of a cyclic hemiacetal of thestructural formula:

wherein A represents an alkali metal atom selected from the groupconsisting of lithium, sodium, and potassium; wherein R and R′ can bethe same or different and are selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, andalkaryl groups containing from 7 to about 18 carbon atoms; with asilicon containing compound of the structural formula:R″_(4-n)SiA′_(n)wherein n represents an integer from 1 to 4; wherein R″ represents analkyl group containing from 1 to about 10 carbon atoms; wherein A′represents a halide atom selected from the group consisting of fluorine,chlorine, bromine, and iodine; wherein said process is conducted at atemperature which is within the range of about −100° C. to about 50° C.

The subject invention also discloses a process for synthesizing amodified silane which comprises reacting the sodium salttetrahydropyran-2-ol; with silicon tetrachloride; wherein said processis conducted at a temperature which is within the range of about −100°C. to about 50° C.

The present invention further discloses a process for synthesizing thealkali metal salt of a cyclic hemiacetal which comprises reacting thecyclic hemiacetal with an alkali metal compound having a structuralformula selected from the group consisting of:R**M*wherein M* is an alkali metal selected from the group consisting of Li,Na, and K; wherein R** is selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, and alkarylgroups containing from 7 to about 18 carbon atoms; wherein said alkylgroups, aryl groups, and alkaryl groups can contain heteroatoms selectedfrom the group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon; wherein said process is conducted in the absence of proticsolvents selected from the group consisting of R″OH; wherein R″ isselected from the group consisting of hydrogen atoms, alkyl groupscontaining from 1 to about 12 carbon atoms, aryl groups containing fromabout 6 to about 18 carbon atoms, and alkaryl groups containing from 7to about 18 carbon atoms; wherein said alkyl groups, aryl groups, andalkaryl groups can contain heteroatoms selected from the groupconsisting of oxygen, sulfur, nitrogen, phosphorus, and silicon; whereinsaid process is conducted at a temperature which is within the range ofabout −100° C. to about 100° C.

The subject invention also discloses a process for synthesizing thesodium salt of a cyclic hemiacetal which comprises reacting the cyclichemiacetal with sodium hydride; wherein said process is conducted in theabsence of protic solvents selected from the group consisting of R″OH;wherein R″ is selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein said alkyl groups,aryl groups, and alkaryl groups can contain heteroatoms selected fromthe group consisting of oxygen, sulfur, nitrogen, phosphorus, andsilicon; wherein said process is conducted at a temperature which iswithin the range of about −100° C. to about 100° C.

The subject invention also reveals a process for synthesizing the sodiumsalt of tetrahydropyran-2-ol which comprises reactingtetrahydropyran-2-ol with sodium hydride; wherein said process isconducted in the absence of protic solvents selected from the groupconsisting of R″OH; wherein R″ is selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, andalkaryl groups containing from 7 to about 18 carbon atoms; wherein saidalkyl groups, aryl groups, and alkaryl groups can contain heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon; wherein said process is conducted at atemperature which is within the range of about −100° C. to about 100° C.

DETAILED DESCRIPTION OF THE SYNTHESIS OF A COATING RESIN

The coating resins of this invention are prepared by free radicalemulsion polymerization. The charge compositions used in the preparationof the latices of the coating resins contain monomers, at least oneemulsifier (soap), such as an α-olefin sulfonate surfactant, and atleast one free radical initiator. The monomer charge composition used insuch polymerizations will typically be comprised of (a) from about 30 toabout 75 weight percent vinyl aromatic monomers, (b) from about 20 toabout 65 weight percent of alkyl acrylate monomers, (c) from about 1 toabout 8 weight percent alkyl propenoic acid monomers, and (d) about 0.5to about 5 weight percent of a reversibly protected silane monomer.

It is preferred for the polymer being synthesized to be comprised offrom about 40 weight percent to about 70 weight percent vinyl aromaticmonomers, from about 25 weight percent to about 55 weight percent alkylacrylate monomers, from about 1.5 weight percent to about 5 weightpercent alkyl propenoic acid monomers and from about 1 weight percent toabout 3 weight percent of a reversibly protected silane monomer. It ismore preferred for the polymer to be comprised of from about 63 weightpercent to about 67 weight percent vinyl aromatic monomers, from about27 weight percent to about 31 weight percent alkyl acrylate monomers,from about 2 weight percent to about 4 weight percent alkyl propenoicacid monomers, and from about 1.5 weight percent to about 2 weightpercent reversibly protected silane monomers.

Some representative examples of vinyl aromatic monomers which can beused include styrene, alpha-methyl styrene and vinyl toluene. Styreneand alpha-methyl styrene are the preferred vinyl aromatic monomers. Dueto its relatively low cost, styrene is the most preferred vinyl aromaticmonomer.

The alkyl acrylate monomers which can be employed have alkyl moietieswhich contain from 2 to about 10 carbon atoms. The alkyl acrylatemonomer will preferably have an alkyl moiety that contains from 3 to 5carbon atoms. Normal-butyl acrylate is a highly preferred alkyl acrylatemonomer.

The alkyl propenoic acid monomers that can be used have the structuralformula:

wherein R represents a hydrogen atom or an alkyl group containing from 1to 4 carbon atoms. The R group can accordingly be represented by theformula —C_(n)H_(2n+1) wherein n is an integer from 0 to 4. Somerepresentative examples of alkyl propenoic acid monomers which can beused include: acrylic acid, methacrylic acid (2-methylpropenoic acid),2-ethylpropenoic acid, 2-propylpropenoic acid and 2-butylpropenoic acid.The preferred alkyl propenoic acid monomers are acrylic acid andmethacrylic acid.

In most cases, it is advantageous to use a combination of both acrylicacid and methacrylic acid as the unsaturated carbonyl compound componentused in making the latex. For instance, the utilization of about 1 toabout 3 weight percent acrylic acid with about 0.5 to about 1.5 weightpercent methacrylic acid results in the latex having improvedfreeze-thaw stability. For example, the utilization of about 2 percentacrylic acid with 1 percent methacrylic acid as the unsaturated carbonylcompound component results in the latex produced being capable ofwithstanding more than five (5) freeze-thaw cycles. It is important forlatices which are shipped through cold regions of the world to have thisimproved freeze-thaw stability.

The reversibly protected silane monomers that can be used are of astructural formula selected from the group consisting of:

wherein m represents an integer from 1 to about 20; wherein X′ groupscan be the same or different; wherein X′ represents an unsaturatedmoiety containing at least one non-aromatic double bond; wherein Q isselected from the group consisting of hydrogen atoms and SiX′₃; whereinR and R′ can be the same or different and are selected from the groupconsisting of hydrogen atoms, alkyl groups containing from 1 to about 12carbon atoms, aryl groups containing from about 6 to about 18 carbonatoms, alkaryl groups containing from 7 to about 18 carbon atoms, alkoxygroups containing from 1 to about 18 carbon atoms, hydroxy groups, andhalide atoms; wherein R* is selected from the group consisting ofhydrogen atoms, alkyl groups containing from 1 to about 12 carbon atoms,aryl groups containing from about 6 to about 18 carbon atoms, andalkaryl groups containing from 7 to about 18 carbon atoms; wherein R,R′, and R* can be bonded together in any combination in cases where R,R′, and R* are not hydrogen atoms, halide atoms, or hydroxy groups;wherein Y represents a moiety selected from the group consisting ofoxygen, sulfur, nitrogen, and phosphorus; wherein Z represents a moietyselected from the group consisting of C(R)R′, oxygen, sulfur, nitrogen,and phosphorus; wherein the contiguous cyclic ring in formulas (1), (2),(3), (4), (5), (6), (7), (8), (9), and (10) can contain heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon in cases where m represents an integer greaterthan 1; wherein the contiguous cyclic ring in formulas (1), (2), (3),(4), (5), (6), (7), (8), (9), and (10) can be saturated or unsaturatedin cases where m represents an integer greater than 1; wherein saidalkyl groups, aryl groups, alkaryl groups, and alkoxy groups can containhalide atoms and heteroatoms selected from the group consisting ofoxygen, sulfur, nitrogen, phosphorus, and silicon.

Some specific examples of reversibly protected silane monomers that canbe used include 3-methacryloxypropylsilane tri-acetal andvinylmethylsilane diacetal.

The charge composition used in the preparation of the latice willcontain a substantial quantity of water. The ratio between the totalamount of monomers present in the charge composition and water can rangebetween about 0.2:1 and about 1.2:1. It is generally preferred for theratio of monomers to water in the charge composition to be within therange of about 0.8:1 and about 1.1:1. For instance, it is verysatisfactory to utilize a ratio of monomers to water in the chargecomposition of about 1:1.

The charge composition will also typically contain from about 0.2 phm(parts per hundred parts of monomer) to about 3 phm of at least oneemulsifier (soap), such as an α-olefin sulfonate soap. It is normallypreferred for α-olefin sulfonate surfactants to be present in thepolymerization medium at a level within the range of about 0.4 phm toabout 2 phm. It is generally more preferred for the charge compositionto contain from about 0.5 phm to about 1 phm of the α-olefin sulfonatesoap.

The use of larger amounts of the α-olefin sulfonate soap in thepolymerization medium leads to better latex stability. However, theutilization of larger amounts of surfactant also leads to greaterblushing in the ultimate coating and consequently less rust andcorrosion resistance.

The free radical aqueous emulsion polymerizations used in preparing thelatice is typically initiated with at least one free radical generator.The free radical generator is normally employed at a concentrationwithin the range of about 0.01 phm to about 1 phm. The free radicalinitiators which are commonly used include the various peroxygencompounds such as potassium persulfate, ammonium persulfate, benzoylperoxide, hydrogen peroxide, di-t-butyl peroxide, dicumyl peroxide,2,4-dichlorobenzoyl peroxide, decanoyl peroxide, lauryl peroxide, cumenehydroperoxide, p-menthane hydroperoxide, t-butyl hydroperoxide, acetylperoxide, methyl ethyl ketone peroxide, succinic acid peroxide, dicetylperoxydicarbonate, t-butyl peroxyacetate, t-butyl peroxymaleic acid,t-butyl peroxybenzoate, acetyl cyclohexyl sulfonyl peroxide and thelike; the various azo compounds such as 2-t-butylazo-2-cyanopropane,dimethyl azodiisobutyrate, azodiisobutylronitrile,2-t-butylazo-1-cyanocyclohexane, 1-t-amylazo-1-cyanocyclohexane and thelike, the various alkyl perketals, such as2,2-bis-(t-butyl-peroxy)butane and the like. Water-solubleperoxygen-free radical initiators are especially useful in such aqueouspolymerizations.

The emulsion polymerization is typically carried out at the temperatureranging between about 125° F. (52° C.) and 190° F. (88° C.). Attemperatures above about 190° F. (88° C.), alkyl acrylate monomers, suchas butyl acrylate, have a tendency to boil. Thus, a pressurized jacketwould be required for heating such alkyl acrylate monomers totemperatures in excess of about 88° C. On the other hand, thepolymerization reaction proceeds at a very slow rate at temperaturesbelow about 125° F. (52° C.). The slow rate of polymerizationexperienced at temperatures below about 125° F. (52° C.) results in thepolymer having a nonuniform distribution of repeat units in itsbackbone. The slow rates of polymerization experienced at such lowtemperatures are also undesirable because they greatly reduce thethroughput of the polymerization reactor.

It is generally preferred for the polymerization temperature to bemaintained within the range of about 150° F. (66° C.) to 180° F. (82°C.). It is generally more preferred for the reaction temperature to becontrolled within the range of about 160° F. (71° C.) to about 170° F.(77° C.). It is important for the polymerization to be conducted at a pHthat is below about 3.5 so that a water-sensitive polymer is notproduced. It is preferred for the pH of the polymerization medium to bemaintained at a level of about 3.0 or less throughout thepolymerization. As the polymerization proceeds, the pH of thepolymerization medium will drop naturally. Thus, good results can beattained by adjusting the pH of the initial monomer charge compositionto within the range of about 3.0 to about 3.5 and allowing thepolymerization to proceed. In such a case, the final pH of thepolymerization medium will be about 1.5 which is highly satisfactory.

In commercial operations, it is typically desirable to add about 15percent to about 25 percent of the monomers in an initial charge. Theinitial charge is then allowed to react for a period of about 30 minutesto about 60 minutes. Then the balance of the monomers to be charged canbe continuously charged into the reaction zone at a rate which issufficient to maintain a reaction temperature within the desiredtemperature range. By continuously adding the monomers to the reactionmedium while maintaining a relatively constant reaction temperature,very uniform polymers can be prepared.

In accordance with the process of this invention, the latex synthesizedis then neutralized with ammonia to a pH within the range of about 7 toabout 10.5. It is normally preferred for the latex to be neutralized toa pH within the range of 8 to 10 and more preferred for the latex to beneutralized to a pH within the range of about 9.0 to about 9.5. This canbe accomplished by simply dispersing ammonia throughout the latex toproduce neutralized latex. The ammonia will normally be in the form ofammonium hydroxide.

The latex formed can be diluted with additional water to theconcentration (solids content) that is desired. This latex can be usedin the preparation of water-reducible coatings using techniqueswell-known to those skilled in the art. Generally, various pigments andplasticizers are added to the latex in the preparation of thewater-reducible coating. Poor adhesion is a problem that is sometimesencountered with water-reducible resins. The adhesion of coatings madewith water-reducible resins to substrates can be greatly improved by theaddition of a plasticizer.

A film-forming, water-reducible composition, such as a paint, can beprepared by mixing the latex, one or more pigments and a plasticizer. Itis not necessary to include a coalescing solvent in the film-forming,water-reducible formulation. For environmental reasons, it is preferrednot to include a coalescing solvent in the formulation. However, a smallamount (0 to about 50 grams per liter) of coalescing solvent can beincluded. In cases where a coalescing solvent is employed, it ispreferable for it to be at least water-miscible and even more preferablefor it to be water-soluble. Of the various coalescing solvents generallyester-alcohols, such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate,are preferred.

It should be noted that the pigment, plasticizer and optionally thecoalescing solvent can be mixed directly with the resin in its wateremulsion or latex. In such an operation, the composite wouldautomatically be in a water-reduced form when sufficient ammonia isused.

Paint formulations can be made utilizing the latices of this invention.Such paint formulations are comprised of one or more pigments and thelatex (water, emulsifier system and resin). Such paints can optionallycontain fillers, plasticizers, stabilizers, defoamers, dryers,fungicides, insecticides, antifouling agents and anticorrosive agents.

Pigments are normally added to paint formulations to impart color andhiding power to the coating. Titanium dioxide is an example of awidely-used pigment which imparts hiding power and a white color.Mineral pigments, such as oxides of iron and chromium, organic pigments,such as phthalocyanine, and active anticorrosive pigments, such as zincphosphate, are representative examples of other widely-used pigments.

Fillers are normally inexpensive materials which are added to the paintformulation to attain the desired consistency and non-settlingcharacteristics. Fillers can also improve the physical properties ofcoatings, such as resistance to cracking and abrasion. Somerepresentative examples of widely utilized fillers include chalks,clays, micas, forms of barites and talcs, and silica.

Driers are chemical compounds, such as salts of cobalt, lead, manganese,barium and zinc, which speed up drying. Stabilizers are chemical agentswhich neutralize the destructive effects of heat and ultraviolet light.Fungicides and insecticides are commonly added to interior and exteriorhouse paints. Antifouling compounds are commonly added to marine paintsto inhibit marine growth. Plasticizers are agents which control thehardness of the film or which impart flexibility.

Of the various plasticizers, it is desired that one be selected which isliquid at room temperature such as 25° C. and have a sufficiently highboiling point, preferably at least 100° C., and even more preferably, atleast 150° C., so that they do not volatilize from the coatingcomposition when applied to a substrate. Plasticizers which containmultiple hydroxyl groups should be avoided because their use can lead toinstability. The plasticizer should enhance the water insolubility of adried coating of the coalesced resin. Further, the plasticizer, ormixture of plasticizers, must be characterized by being compatible withthe resin itself. For this characterization, a solubility parameter inthe range of about 8 to about 16 is required. Such solubility parameteris of the type described in The Encyclopedia of Polymer Science andTechnology, Volume 3, Page 854, 1965, John Wiley and Sons, Inc., whichis simply determined by the equationσ=(ΣF)/V=F/MW/d whereσ=solubility parameter

F=sum of the pertinent molar attraction constants of groups determinedby Small, P A [(J Appl Chem 3, 71, (1953)]

V=Molar volume at 25° C.

MW=molecular weight

d=density at 25° C.

Various plasticizers can be used for this purpose. They can, forexample, be of the type listed in the Federation Series on CoatingsTechnology, Unit Twenty-two, entitled “Plasticizers,” published April1974, so long as they fulfill the melting point, boiling point andcompatibility requirements. Some representative examples of preferredplasticizers include: butyl benzyl phthalate, blends of diethyleneglycoldibenzoate and dipropylene glycol dibenzoate, and2,2,4-trimethyl-1,3-pentanediol diisobutyrate.

Representative of various plasticizers are cyclic plasticizers such asphosphoric acid esters, phthalic anhydride esters and trimellitic acidesters as well as N-cyclohexyl-p-toluene sulfonamide, dibenzyl sebacate,diethylene glycol dibenzoate, di-t-octylphenylether, dipropane dioldibenzoate, N-ethyl-p-toluene sulfonamide,isopropylidenediphenoxypropanol, alkylated naphthalene, polyethyleneglycol dibenzoate, o-p-toluene sulfonamide, trimethylpentanedioldibenzoate and trimethylpentanediol monoisobutyrate monobenzoate.

Representative of various acyclic plasticizers are adipic acid esters,azelaic acid esters, citric acid esters, acetylcitric acid esters,myristic acid esters, phosphoric acid esters, ricinoleic acid esters,acetylricinoleic acid esters, sebacic acid esters, stearic acid esters,epoxidized esters, as well as 1,4-butane diol dicaprylate, butoxyethylpelargonate di[(butoxyethoxy)ethoxy] methane, dibutyl tartrate,diethylene glycol dipelargonate, diisooctyl diglycolate, isodecylnonanoate, tetraethylene glycol di(2-ethylbutyrate), triethylene glycoldi(2-ethyl-hexanoate), triethylene glycol dipelargonate and2,2,4-trimethyl-1,3-pentane diol diisobutyrate.

Additional various plasticizers, cyclic, acyclic, and otherwise, includechlorinated paraffins, hydrogenated terphenyls, substituted phenols,propylene glycols, polypropylene glycol esters, polyethylene glycolesters, melamines, epoxidized soys, oils, melamines, liquid,hydrogenated abietate esters, epoxytallate esters, alkyl phthalyl alkylglycolates, sulfonamides, sebacate esters, aromatic epoxies, aliphaticepoxies, liquid poly(α-methyl styrene), maleate esters, mellitateesters, benzoates, benzyl esters, tartrates, succinates, isophthalates,orthophthalates, butyrates, fumarates, glutarates, dicaprylates,dibenzoates and dibenzyl esters. It is to be appreciated that relativelylow molecular weight polymers and copolymers derived from monoolefinscontaining 4 to 6 carbon atoms, mixtures of diolefins and monoolefinscontaining 4 to 6 carbon atoms as well as such hydrocarbons andhydrocarbon mixtures with styrene and/or α-methyl styrene can also beused.

The preferred esters are prepared from the reaction of carboxylic anddicarboxylic acids including fatty acids, such as the phthalic acids,benzoic acid, dibenzoic acid, adipic acid, sebacic acid, stearic acid,maleic acid, tartaric acid, succinic acid, butyric acid, fumaric acidand glutaric acid with hydrocarbon diols, preferably saturatedhydrocarbon diols, having about 7 to 13 carbon atoms.

Representative of various phosphoric acid esters are cresyl diphenylphosphate, tricresyl phosphate, dibutyl phenyl phosphate, diphenyl octylphosphate, methyl diphenyl phosphate, tributyl phosphate, triphenylphosphate, tri(2-butoxyethyl)phosphate, tri(2-chloroethyl)phosphate,tri-2(chloropropyl)phosphate and trioctyl phosphate.

Representative of various phthalic anhydride esters are butyl octylphthalate, butyl 2-ethylhexyl phthalate, butyl n-octyl phthalate,dibutyl phthalate, diethyl phthalate, diisodecyl phthalate, dimethylphthalate dioctyl phthalates, di(2-ethylhexyl)phthalate, diisooctylphthalate, di-tridecyl phthalate, n-hexyl n-decyl phthalate, n-octyln-decyl phthalate, alkyl benzyl phthalate,bis(4-methyl-1,2-pentyl)phthalate, butyl benzyl phthalate, butylcyclohexyl phthalate, di(2-butoxyethyl)phthalate, dicyclohexyl isodecylphthalate, dicyclohexyl phthalate, diethyl isophthalate, di n-heptylphthalate, dihexyl phthalate, diisononyl phthalate,di(2-methoxyethyl)phthalate, dimethyl isophthalate, dinonyl phthalate,dioctyl phthalates, dicapryl phthalate, di(2-ethylhexyl)isophthalate,mixed dioctyl phthalates, diphenyl phthalate, 2-(ethylhexyl)isobutylphthalate, butyl phthalyl butyl glycolate, ethyl (and methyl)phthalylethyl glycolate, polypropylene glycol bis(amyl)phthalate, hexyl isodecylphthalate, isodecyl tridecyl phthalate and isooctyl isodecyl phthalate.

Representative of trimellitic acid esters are triisooctyl trimellitate,tri-n-octyl n-decyl trimellitate, trioctyl trimellitate,tri(2-ethylhexyl)trimellitate, tri-n-hexyl n-decyl trimellitate,tri-n-hexyl trimellitate, triisodecyl trimellitate and triisononyltrimellitate.

Representative of various adipic acid esters aredi[2-(2-butoxyethoxy)ethyl]adipate, di(2-ethylhexyl)adipate, diisodecyladipate, dioctyl adipates (including diisooctyl adipate) n-hexyl n-decyladipate, n-octyl n-decyl adipate and di-n-heptyl adipate.

Representative examples of sebacic acid esters are dibutyl sebacate,di(2-ethylhexyl)sebacate, dibutoxyethyl sebacate, diisooctyl sebacateand diisopropyl sebacate.

Representative examples of azelaic acid esters aredi(2-ethylhexyl)acelate dicyclohexyl acelate, diisobutyl azelate anddiisooctyl azelate. In the practice of this invention, thewater-reducible composition of resin, plasticizer and coalescingsolvent, if used, is water-reduced by neutralizing the carboxyl groupsof the resin with ammonia and mixing with water. The resultingdispersion or solution can generally be characterized by being stablewithout appreciable, if any, precipitation of the resin for a period ofat least thirty (30) days and preferably for a period of at least 365days or more at about 25° C.

Generally, for the purpose of this invention, about 100 to about 400parts by weight water are used per 100 parts by weight neutralizedresin, although more or less water can usually be used depending onwhether a high or low viscosity dispersion or solution is desired orwhether a high or low solids content is desired. It also depends on thetype and amount of coalescing solvent (if any) and plasticizer used. Thewater-reduced coating composition, as an aqueous dispersion or solution,is applied as a coating onto a suitable substrate such as wood, masonry,various plastics and various metals. The water, ammonia and coalescingsolvent are evaporated from the coating, usually at a temperature in therange of about 20° C. to about 100° C., preferably about 25° C. to about50° C. to leave a substantially water-insoluble coating of the coalescedresin and plasticizer. Generally, such a coating can be prepared andapplied without the need for additional hardening agents or curatives todecrease the water sensitivity.

Therefore, it is an important feature of this invention that a durablecrosslinked coating is formed on a substrate through the preparation ofa particular resin having balanced hydrophilic and hydrophobic elements,preferably with a further balance of hard and soft segments, and theformation of a water-reduced composition of such resin with acombination of pigment and compatible plasticizer. The crosslinkingoccurs rapidly at ambient temperatures without the need for addingseparate curatives or crosslinking agents. Improved adhesion to metaland glass substrates is also attained.

This invention is illustrated by the following examples that are merelyfor the purpose of illustration and are not to be regarded as limitingthe scope of the invention or the manner in which it can be practiced.Unless specifically indicated otherwise, parts and percentages are givenby weight.

EXAMPLE 1

General. All reagents were purchased from Gelest unless otherwise notedand used without further purification. Tetrahydropyran-2-ol was preparedaccording to the literature by the acid catalyzed hydrolysis ofdihydropyran (see Bartness J. E.; Hays R. L.; Caldwell G.; J. Am. Chem.Soc. 1981, 103, 1338 and March J. in Advanced Organic Chemistry, FourthEd., Wiley Interscience, N.Y.; p 764). The 0.5 M solution of NaOMe inmethanol was purchased from Aldrich.

Experiment 1a

Tetrahydropyran-2-ol (25 g, 0.24 mol) andn-octadecyldimethylmethoxysilane (82 g, 0.24 mol) where reacted withstirring in the presence of a methanol solution of NaOMe (1 g, 0.5 M)for 2 h at 30° C. and reduced pressure (50 Torr). Methanol formed in thereaction and from the NaOMe solution were distilled and the reactionproduct neutralized with HCl. The n-octadecyldimethylsilane-acetalcompound was obtained as a colorless liquid by ¹H-NMR, ¹³C-NMR,²⁹Si-NMR.

Experiment 1b

Tetrahydropyran-2-ol (49 g, 0.48 mol) and vinylmethyldiethoxysilane (39g, 0.24 mol) where reacted with stirring in the presence of a methanolsolution of NaOMe (1 g, 0.5 M) for 2 h at 30° C. and reduced pressure(50 Torr). Ethanol formed in the reaction and the methanol from theNaOMe solution were distilled and the reaction product neutralized withHCl. The vinylmethylsilane di-acetal monomer was obtained as a colorlessliquid in high purity by ¹H-NMR, ¹³C-NMR, ²⁹Si-NMR.

Experiment 1c

Tetrahydropyran-2-ol (74 g, 0.72 mol) and3-methacryloxypropyltrimethoxysilane (60 g, 0.24 mol) where reacted withstirring in the presence of a methanol solution of NaOMe (1 g, 0.5 M)for 2 h at 30° C. and reduced pressure (50 Torr). Methanol formed in thereaction and from the NaOMe solution were distilled and the reactionproduct neutralized with HCl. The 3-methacryloxypropylsilane tri-acetalmonomer was obtained as a colorless liquid in high purity by ¹H-NMR,¹³C-NMR, ²⁹Si-NMR.

Experiment 1d

Tetrahydropyran-2-ol (98 g, 0.96 mol) and tetraethylorthosilicate (50 g,0.24 mol) where reacted with stirring in the presence of a methanolsolution of NaOMe (1 g, 0.5 M) for 2 h at 30° C. and reduced pressure(50 Torr). Ethanol formed in the reaction and the methanol from theNaOMe solution were distilled and the reaction product neutralized withHCl. The silane tetra-acetal compound was obtained as a colorless liquidin high purity by ¹H-NMR, ¹³C-NMR, ²⁹Si-NMR.

EXAMPLE 2

General. The sodium lauryl sulfate was purchased from Proctor andGamble. The styrene was purchased from Sterling Chemical. The butylacrylate and ammonium hydroxide were purchased from Aldrich. Themethacrylic acid was purchased from Du Pont. The potassium persulfateand ammonium persulfate were purchased from FMC. All materials were usedas received without further purification.

Polymerization Procedure. To a 1 gal glass bowl reactor that has beenevacuate to less than 25 in Hg for 30 min add the Buffer Solution andthe Stage 1 Monomers. Heat to 170° F. and add the Activator Solution.Check the reactor solids after 30 min. If the solids are over 18 wt %add ammonium hydroxide to yield a pH of 9.0. Remove a sample anddetermine its pH. If the pH is below 9.0 add additional ammoniumhydroxide. If solids are below 19 wt % continue the polymerization foran additional 30 min and recheck the polymer solids. The polymerizationwill overheat to 190° F.–200° F. (88° C.–93° C.). If overheating occursadjust the reactor temperature to 170° F. (77° C.) and begin adding theStage 2 Monomers. Adjust the flow rate so that the monomer is added overa period of 2.5 hours. Continue the polymerization at 170° F. (77° C.)until the residual styrene level drops below 500 ppm. If the residualstyrene remains above 500 ppm, add 0.1 parts of ammonium persulfate in200 ml of water and continue the polymerization until the residualstyrene is below 500 ppm. Allow the latex to cool before removing itfrom the reactor. Note that agitation should consist of 2 AFT's rotating200 rpm.

MEK Rub Testing Procedure. The latex material obtained in thepolymerizations was applied by brush on a block on non-porous masonryand allowed to cure at room temperature for 12 h. The resulting film wassubjected to methyl ethyl ketone (MEK) rub testing.

Experiment 2a Recipe

Buffer Solution

-   -   RO Water: 1472.59 g    -   Sodium Lauryl Sulfate (28% active): 3.35 g

Stage 1 Monomers

-   -   Styrene: 126.88 g    -   Butyl Acrylate: 235.63 g    -   Methacrylic Acid: 37.50 g

Activator Solution

-   -   Water: 125 g    -   Potassium Persulfate: 3.13 g

Stage 2 Monomers

-   -   Styrene: 297.50 g    -   Butyl Acrylate: 552.50 g        Data/Results:

Solids: 41.6 wt %

pH: 8.40

Brookfield Viscosity: 20

MEK Rub Test (Reciprocations): 3

Experiment 2b Recipe

Buffer Solution

-   -   RO Water: 1472.59 g    -   Sodium Lauryl Sulfate (28% active): 3.35 g

Stage 1 Monomers

-   -   Styrene: 126.88 g    -   Butyl Acrylate: 235.63 g    -   Methacrylic Acid: 37.50 g

Activator Solution

-   -   Water: 125 g    -   Potassium Persulfate: 3.13 g

Stage 2 Monomers

-   -   Styrene: 293.75 g    -   Butyl Acrylate: 531.25 g    -   The 3-methacryloxypropylsilane tri-acetal monomer from        Experiment 1c: 25.0 g        Data/Results:

Solids: 41.6 wt %

pH: 8.44

Brookfield Viscosity: 25

MEK Rub Test (Reciprocations): 35

EXAMPLE 3

General. All reagents were purchased from Alrich unless otherwise notedand used without further purification. Tetrahydropyran-2-ol was preparedaccording to the literature by the acid catalyzed hydrolysis ofdihydropyran (see Bartness J. E.; Hays R. L.; Caldwell G.; J. Am. Chem.Soc. 1981, 103, 1338 and March J. in Advanced Organic Chemistry, FourthEd., Wiley Interscience, N.Y.; p 764). All procedures were conductedunder nitrogen or in an inert atmosphere dry box using standard Schlencktechniques.

Experiment 3a

A solution of tetrahydropyran-2-ol (21 g, 0.21 mol) in anhydrous diethylether (100 mL) was added dropwise to a slurry of NaH (4.7 g, 0.20 mol)in anhydrous diethyl ether (100 mL) with stirring at ca. 25° C. over aperiod of 2 hours. The resulting white precipitate was filtered andwashed with anhydrous diethyl ether (60 mL), collected, and placed undervacuum until reaching a constant weight. The sodium salt oftetrahydropyran-2-ol (NaO-THP) was obtained as a white solid in 86%yield and characterized by ¹H-NMR and ¹³C-NMR.

Experiment 3b

A solution of SiCl₄ (3.4 g, 0.02 mol) in anhydrous diethyl ether (75 mL)was added dropwise to a slurry of NaO-THP (10 g, 0.081 mol) in anhydrousdiethyl ether (75 mL) with stirring at −78° C. over a period of 2 hours.The resulting heterogeneous mixture was filtered. The filtrate wascollected and placed under vacuum until reaching a constant weight. Thesilane tetra-acetal compound was obtained as a colorless liquid andcharacterized by ¹H-NMR, ¹³C-NMR, and ²⁹Si-NMR.

Variations in the present invention are possible in light of thedescription of it provided herein. While certain representativeembodiments and details have been shown for the purpose of illustratingthe subject invention, it will be apparent to those skilled in this artthat various changes and modifications can be made therein withoutdeparting from the scope of the subject invention. It is, therefore, tobe understood that changes can be made in the particular embodimentsdescribed which will be within the full intended scope of the inventionas defined by the following appended claims.

EXAMPLE 4 Experiment 4a Polybutylacrylate

Polybutylacrylate was prepared by emulsion polymerization in a 8 ozglass bottle sealed with a screw cap which contained a rubber gasket anda Teflon liner. The soap solution for the polymerization was preparedfrom 4.3 g dodecylbenzene sulfonic acid neutralized with ammoniumhydroxide in 150 g water treated by reverse osmosis. The soap solutionwas charged to the bottle followed by 36 g of butylacrylate. Followingthe charging of the bottle, the head space was purged with nitrogen. Thebottles were placed in a polymerization bath controlled at a temperatureof 25° C. The bottle was allowed to rotate end-over-end for 30 minutesto disperse the butylacrylate. After 30 minutes, 2 mls of an activatorsolution containing 22 g of reverse osmosis water, 0.088 g ferric sodiumEDTA, and 0.194 g sodium formaldehyde sulfoxylate was charged to thebottle through syringe and the bottle rotated. After 10 minutes, 0.219 gof pinane hydroperoxide was charged to the bottle by syringe to initiatethe polymerization and allowed to rotate for 16 hours.

Experiment 4b Polybutylacrylate-co-MethacryloxypropylTrimethoxysilane˜10 mole %

The same procedure employed as in Comparative Experiment 4a with theonly change being that 30.2 g butylacrylate and 5.9 g methacryloxypropyltrimethoxysilane (A-174)were charged as the monomer solution.

Experiment 4c Polybutylacrylate-co-Methacryloxypropyl Trimethoxysilane˜5mole %

The same procedure employed as in Comparative Experiment 4a with theonly change being that 32.8 g butylacrylate and 3.2 g methacryloxypropyltrimethoxysilane (A-174)were charged as the monomer solution.

Experiment 4d Polybutylacrylate-co-MethacryloxypropylTrimethoxysilane˜2.5 mole %

The same procedure employed as in Comparative Experiment 4a with theonly change being that 34.3 g butylacrylate and 1.7 g methacryloxypropyltrimethoxysilane (A-174) were charged as the monomer solution.

Experiment 4e Polybutylacrylate-co-Modified silane monomer˜10 mole %

The same procedure employed as in Comparative Experiment 4a with theonly change being that 26.5 g butylacrylate and 9.5 g of the followingmonomer were charged as the monomer solution.

Experiment 4f Polybutylacrylate-co-protected A174˜5 mole %

The same procedure employed as in Comparative Experiment 4a with theonly change being that 30.5 g butylacrylate and 5.5 g of the modifiedsilane containing monomer above were charged as the monomer solution.

Experiment 4g Polybutylacrylate-co-protected A174˜2.5 mole %

The same procedure employed as in Comparative Experiment 4a with theonly change being that 33.05 g butylacrylate and 3.0 g of the modifiedsilane containing monomer above were charged as the monomer solution.

Swelling Test

Latexes were cast on Teflon sheets and allowed to dry at roomtemperature for three days. Approximately 5 gms of the dried film wasplaced in 50 mls of toluene and allowed to reach an equilibrium weight.The ratio of the swollen weight to the initial weight was taken as apercentage to determine the degree of swelling of the films.

Aging test

The latex was aged by allowing to stand in a sealed bottle in an ovencontrolled at 50° C. for thirty days without agitation.

Polymerization Results Mole wt % n-BA wt % Silane % Silane % ConversionExperiment 4a 100 0 0 100 Experiment 4b 83.77 16.23 9.23 97.0 Experiment4c 91.17 8.83 4.83 98.0 Experiment 4d 95.39 4.61 2.55 98.9 Experiment 4e73.65 26.35 9.21 87.6 Experiment 4f 84.83 15.17 4.80 92.2 Experiment 4g91.81 8.19 2.32 94.1

As shown in the table, the conversion of the polymerizations employingthe modified silane monomers were less (87%–94%) than the comparativeexamples (97%–100%).

Swelling Results Mole % Silane Swelling wt % gain Experiment 4a 0Dissolved Experiment 4b 9.23 130 Experiment 4c 4.83 156 Experiment 4d2.55 278 Experiment 4e 9.21 236 Experiment 4f 4.80 259 Experiment 4g2.32 393

As expected, the degree of swelling decreases as the content of thesilane monomers (A174, modified silane-containing monomer) decreases. Itis expected that the difference in the degree of swelling at similarsilane monomer loading levels is due to incomplete incorporation of themodified silane containing monomer.

Aging Results Swelling % wt Mole % Silane Swelling Time gainConversionExperiment 4b 9.23  0 days 130 15 days 276 30 days 238 Experiment 4e9.21  0 Days 226 15 days 184 30 days 145

The aging results demonstrate the inability of the A-174 monomer toremain stable in an aqueous environment for prolonged periods of time.Initially, the degree of swelling increases indicating the loss offunctionality for crosslinking, likely by intra-particle crosslinking.At 30 days, the extent of crosslinking within the bottle is significantenough that the degree of swelling measurement is very dependent uponthe ability of the latex to form a cohesive film.

EXAMPLE 5 Adhesive Experimental

General. The following procedure was used to prepare the test samples.The following modified silane reticulating agent was predispersed in amixture of Igepal CO-880 and 10 wt % NH₄OH:

Robond PS-94 was then added and the resulting mixture coated onto a 2 mLpolyester sheet using a 40 Mayer Rod. The coated sheets were then driedat 150° F. for 8 minutes. Igepal CO-880 was purchased from GAFCorporation. Robond PS-94 was obtained from Rohm and Haas Company.

Test 10% Sample Reticulating Agent Igepal CO-880 NH₄OH Robond PS-94 1  0 g 0.12 g 3 g 50 g 2 0.66 g 0.12 g 3 g 50 g 3  1.3   0.24   6 g 50 g

All experiments were conducted under standard laboratory conditions asset forth in ASTM D3924. The Probe Tack test was conducted according toASTM D2979. The Peel Adhesion test was performed using stainless steeland was conducted according to PSTC-1. The Shear Adhesion FailureTemperature test was performed using stainless steel and was conductedaccording to PSTC Appendage B. The modified silane reticulating agentwas prepared using the same procedure as Example 3, Experiment 3b withthe following changes. A solution of bis(trichlorosilyl)octane (23.25 g,0.061 mol) in anhydrous diethyl ether (200 mL) was added dropwise to aslurry of NaO-THP (50.49 g, 0.3661 mol) in anhydrous diethyl ether (200mL) with stirring at −78° C. over a period of 2 hours. The resultingheterogeneous mixture was filtered. The filtrate was collected andplaced under vacuum until reaching a constant weight. The modifiedsilane reticulating agent was obtained as a vicous liquid andcharacterized by ¹H-NMR, ¹³C-NMR, and ²⁹Si-NMR.

Results.

Probe Tack:

Test Polyken Probe Tack (grams) Sample 1 2 3 4 5 6 Ave S Deviation 1 657617 624 676 634 599 635 27.9 2 567 564 529 589 575 600 571 24.5 3 547487 509 516 479 451 498 33.3

These test results show that the modified silane reticulating agentreduces tack in increasing amount, thus demonstrating increased cure andcrosslinking over the control sample which did not contain the modifiedsilane reticulating agent.

Experiment Peel Adhesion:

PSTC-1 Peel Adhesion (lbs/inch Test width) Sample 1 2 3 Average SDeviation 1 1.69 1.54 1.50 1.58 0.10 2 1.84 1.85 1.88 1.86 0.02 3 1.991.85 1.87 1.90 0.08

These test results show that the modified silane reticulating agentincreases adhesion, in increasing amount compared to the control samplewhich did not contain the modified silane reticulating agent.

Shear Adhesion Failure Temperature:

Test Shear Adhesion Failure Temperature (deg F.) Sample 1 2 Average SDeviation 1 267.0 266.0 266.5 0.7 2 >400 >400 >400 0.0 3 259.0 261.0260.0 1.4

These test results show that the modified silane reticulating agentincreases the temperature at which adhesion failure occurs and furthershows that this property is only improved at lower levels of themodified silane reticulating agent.

1. An organometallic compound having a structural formula selected fromthe group consisting of:

wherein M represents an atom selected from the group consisting of Ge,Sn, Pb, Ti, and Zr; wherein n represents an integer from 1 to 4; whereinm represents an integer from 1 to about 20; with the proviso that m canrepresent the integer 0 for structures of formula (3) wherein Zrepresents the group C(R)R′; wherein X groups can be the same ordifferent; wherein X represents a chemical moiety; wherein R, R′, and R″can be the same or different and are selected from the group consistingof hydrogen atoms, alkyl groups containing from 1 to about 12 carbonatoms, aryl groups containing from about 6 to about 18 carbon atoms,alkaryl groups containing from 7 to about 18 carbon atoms, alkoxy groupscontaining from 1 to about 18 carbon atoms, hydroxy groups, and halideatoms; wherein R* is selected from the group consisting of hydrogenatoms, alkyl groups containing from 1 to about 12 carbon atoms, arylgroups containing from about 6 to about 18 carbon atoms, and alkarylgroups containing from 7 to about 18 carbon atoms; wherein R, R′, R″,and R* can be bonded together in any combination in cases where R, R′,R″, and R* are not hydrogen atoms, halide atoms, or hydroxy groups;wherein Y represents a moiety selected from the group consisting ofC(R)R′, oxygen, sulfur, nitrogen, and phosphorus; wherein Y′ representsa moiety selected from the group consisting of oxygen, sulfur, nitrogen,and phosphorus, wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; with theproviso that Y and Z can not both represent the moiety C(R)R′; whereinthe contiguous cyclic ring in formulas (1) and (3) can containheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon in cases where m represents an integergreater than 1; wherein the contiguous cyclic ring in formulas (1) and(3) can be saturated or unsaturated in cases where m represents aninteger greater than 1; wherein said alkyl groups, aryl groups, alkarylgroups, and alkoxy groups can contain halide atoms and heteroatomsselected from the group consisting of oxygen, sulfur, nitrogen,phosphorus, and silicon.
 2. An organometallic compound as specified inclaim 1 wherein the organometallic compound is of the structuralformula:


3. An organometallic compound as specified in claim 2 wherein at leastone of R, R′, and R″ is a hydroxyl group.
 4. An organometallic compoundas specified in claim 1 wherein the organometallic compound is of thestructural formula:


5. An organometallic compound as specified in claim 1 wherein theorganometallic compound is of the structural formula:


6. An organometallic compound as specified in claim 5 wherein at leastone of R, R′, and R″ is a hydroxyl group.
 7. An organometallic compoundas specified in claim 1 wherein the organometallic compound is of thestructural formula:


8. An organometallic compound as specified in claim 1 wherein at leastone of R, R′, and R″ is a hydroxyl group.
 9. An organometallic compoundhaving a structural formula selected from the group consisting of:

wherein M represents an atom selected from the group consisting of Ge,Sn, Pb, Ti, and Zr; wherein in represents an integer from 1 to about 20;wherein X groups can be the same or different; wherein X represents achemical moiety; wherein Q is selected from the group consisting ofhydrogen atoms and MX₃; wherein R and R′ can be the same or differentand are selected from the group consisting of hydrogen atoms, alkylgroups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, alkaryl groupscontaining from 7 to about 18 carbon atoms, alkoxy groups containingfrom 1 to about 18 carbon atoms, hydroxy groups, and halide atoms;wherein R* is selected from the group consisting of hydrogen atoms,alkyl groups containing from 1 to about 12 carbon atoms, aryl groupscontaining from about 6 to about 18 carbon atoms, and alkaryl groupscontaining from 7 to about 18 carbon atoms; wherein R, R′, and R* can bebonded together in any combination in cases where R, R′, and R* are nothydrogen atoms, halide atoms, or hydroxy groups; wherein Y represents amoiety selected from the group consisting of oxygen, sulfur, nitrogen,and phosphorus; wherein Z represents a moiety selected from the groupconsisting of C(R)R′, oxygen, sulfur, nitrogen, and phosphorus; whereinthe contiguous cyclic ring in formulas (5), (6), (7), (8), (9), (10),(11), (12), (13), and (14) can contain heteroatoms selected from thegroup consisting of oxygen, sulfur, nitrogen, phosphorus, and silicon incases where m represents an integer greater than 1; wherein thecontiguous cyclic ring in formulas (5), (6), (7), (8), (9), (10), (11),(12), (13), and (14) can be saturated or unsaturated in oases where mrepresents an integer greater than 1; wherein said alkyl groups, arylgroups, alkaryl groups, and alkoxy groups can contain halide atoms andheteroatoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, and silicon.
 10. An organometallic compound asspecified in claim 9 wherein the organometallic compound is of thestructural formula:


11. An organometallic compound as specified in claim 9 wherein theorganometallic compound is of the structural formula:


12. An organometallic compound as specified in claim 9 wherein theorganometallic compound is of the structural formula:


13. An organometallic compound as specified in claim 9 wherein theorganometallic compound is of the structural formula:


14. An organometallic compound as specified in claim 9 wherein theorganometallic compound is of the structural formula:


15. An organometallic compound as specified in claim 9 wherein theorganometallic compound is of the structural formula:


16. An organometallic compound as specified claim 9 wherein theorganometallic compound is of the structural formula:


17. An organometallic compound as specified in claim 9 wherein theorganometallic compound is of the structural formula:


18. An organometallic compound as specified in claim 9 wherein theorganometallic compound is of the structural formula:


19. An organometallic compound as specified in claim 9 wherein theorganometallic compound is of the structural formula:


20. An organometallic compound as specified in claim 9 wherein at leastone of R, R′, and R″ is a hydroxyl group.